EP0876890B1 - Mouldings, process and apparatus for producing the same - Google Patents

Abstract

Moulded components are made of a hardenable binder which contains one or more granular fillers, by first placing the filler in the mould and then introducing a low viscosity fluid into the mould while it is being vented. The fluid is essentially immiscible and inert in relation to the binder. The fluid is then displaced in the mould by the liquid binder which is hardened, after which the component is removed from the mould.

Description

The invention relates to novel moldings based on a hardened plastic binder containing one or more contains granular fillers, preferably of low density, as well as methods and devices for their production, furthermore their use, in particular as building and construction materials.

The introduction of granular solids or aggregates into a binder, e.g. from the construction industry is known, by mixing the binder with the additives, subsequent shaping and hardening. The bringing in of the hydraulically curing binder with the addition in the molding space is e.g. by free flow with simultaneous Compression by shaking or pressure on the inflowing mass. When using a closed The shape into which the molding compound is poured can be made according to a method according to DE 24 55 634 by evacuating the mold the casting process is accelerated and the material is compressed more become. In addition, the shape with a rough surcharge prefilled and the pressure drop compared to the atmospheric Pressure to fill the mold.

Similar techniques are used to process casting resins known, for example the foaming of a filler filled mold with reaction foams made of polyurethane or Phenolic resin (DE 17 04 853).

Curable molding compounds, such as casting resins based on polyesters, Poly (meth) acrylates (liquid prepolymers) or Epoxy resins are known to be used with or without fillers an evacuated room or in a closed, evacuated Form with the support of the atmospheric external pressure in Molds filled (DE 1 146 245; DE 143 624).

Finally, the centrifugal force is also used to fill molds exploited. Around a fine-grained filler (e.g. micro hollow glass spheres) in a thin resin like a Epoxy resin or a polyester resin, to bring in from it To produce moldings, a mold is filled with the filler, then covered with the liquid resin and centrifuged becomes. The resin penetrates at the same time Ventilation in the empty spaces formed by the filler and forms a largely bubble-free, lightweight material (EP 0 151 461).

The production and processing of curable W / O emulsions, the monomers emulsifiable with water in the oil phase and / or casting resins, together with granular solids, are also known (DE 32 41 798, U.S. 5,033,950); with this procedure the solids are mixed with a W / O emulsion, what after shaping in open cast or after casting the mass is cured under a pressure. Of considerable The disadvantage of these processes is the mixing process, which is a setting of a short pot life and a quick one Curing allowed only with high equipment expenditure, furthermore the emission of monomers and the relatively high amounts of Residues from the mixing process.

It has therefore not previously been possible to make W / O emulsions finely porous Curing moldings, especially to form a matrix with granular solids. The prerequisite for this is that the disperse distribution of the Water in the resin component over the processing and Hardening process is retained. That's why they're good stabilized W / O emulsion and quick and gentle processing, if possible in a closed system, preconditions for the practical applicability of such W / O emulsions.

W / O emulsions, especially those with a higher water content, are in usually thixotropic. The application of pressure therefore brings no advantages, especially since the pressure effect when discharging into a form packed with granular fillers very quickly exhausted. Experiments have shown that negative pressure in one Effective pressure drop easily for extracting water from the Emulsion leads.

The problems described can be solved with the known methods do not overcome.

The object of the invention is therefore to provide molded plastic articles, which contain granular fillers, as well as a method and to provide a device for their manufacture, also the use of the moldings as materials, in particular as molded parts for building and construction purposes. In doing so the use of emulsifiable, preferably with water emulsifiable, hardenable resins as a binder matrix become.

After W / O emulsions in the outer, continuous phase consist of resin and / or monomers, it was assumed that a good bond with fillers only by mixing in the dry Solids to ensure the emulsion. Surprised Tests have shown that this assumption, when used of resins without adding water, not without further on water-emulsifiable resins in the form of W / O emulsions is transferable.

The task is solved by the independent claims. The dependent claims relate to advantageous embodiments the conception of the invention.

• dem Einbringen des bzw. der kornförmigen Füllstoffe sowie eines flüssigen härtbaren Bindemittels in eine Form,
• dem Härten des Bindemittels in der Form und
• der Entnahme des gebildeten Formkörpers aus der Form;

es ist gekennzeichnet durch Vornahme folgender Verfahrensschritte in der angegebenen Reihenfolge:

(A) Einbringen des kornförmigen Füllstoffs bzw. der kornförmigen Füllstoffe in die Form,

(B) Auffüllen der Form mit einer niedrigviskosen, mit dem Bindemittel nicht mischbaren oder weitgehend nicht mischbaren Flüssigkeit, die gegenüber dem Bindemittel inert oder im wesentlichen inert ist, unter Entlüftung der Form,

(C) Ersetzen der Flüssigkeit in der Form durch das flüssige härtbare Bindemittel,

(D) Härten des Bindemittels
und

(E) Entnahme des gebildeten Formkörpers aus der Form.

The process according to the invention for the production of moldings based on a hardened binder which contains one or more granular fillers is based on

• the introduction of the granular filler (s) and a liquid curable binder into a mold,
• the hardening of the binder in the mold and
• the removal of the formed body from the mold;

it is characterized by performing the following process steps in the order given:

(A) introducing the granular filler or fillers into the mold,

(B) filling the mold with a low-viscosity liquid which is immiscible or largely immiscible with the binder and which is inert or essentially inert to the binder, with venting of the mold,

(C) replacing the liquid in the mold with the liquid curable binder,

(D) hardening the binder
and

(E) Removing the formed body from the mold.

The inert liquid, preferably water, is used in the invention Process as a kind of placeholder for that later introduced into the mold resin system that the inert Fluid then replaced. This can be bubble-free Produce binder matrices or moldings.

According to an advantageous embodiment, step B the inert liquid under hydrostatic pressure or under Pump pressure by running in from above or from below introduced the shape.

According to a particularly simple embodiment of the invention Steps A and B can also be carried out together be done in a single step, for example, by a previously prepared dispersion or Suspension of the filler in the inert liquid in the Form is introduced, with venting.

This procedure is particularly useful when it is difficult to wet Fillers with air bubbles on their surface can, advantageous.

(a) das Bindemittel wird unter hydrostatischem Druck oder unter Pumpdruck von oben in die Form eingeführt, und die inerte Flüssigkeit wird im unteren Teil der Form austreten gelassen oder abgepumpt,
oder

(b) das Bindemittel wird unter hydrostatischem Druck oder unter Pumpdruck oder durch Ansaugen von unten in die Form eingeführt, und die inerte Flüssigkeit wird im oberen Teil der Form austreten gelassen oder abgepumpt.

In the context of the invention, step C is advantageously carried out as follows:

(a) the binder is introduced into the mold from above under hydrostatic pressure or under pump pressure, and the inert liquid is let out or pumped off in the lower part of the mold,
or

(b) the binder is introduced into the mold under hydrostatic pressure or under pump pressure or by suction from below, and the inert liquid is let out or pumped out in the upper part of the mold.

In both cases, the inert liquid is introduced by the Binder replaced or displaced.

Is advantageous in the context of the invention in step C as Binder uses a polymerizable resin system that one or more polymerizable monomers and optionally contains one or more polymerizable prepolymers.

In the method according to the invention, are advantageously suitable as Binder polyester resin systems, epoxy resin systems as well (Meth) acrylate resin systems.

According to a particularly preferred embodiment of the invention In step C a binder is used in the process Form of a water-in-oil emulsion used, the oil phase contains or from the binder or binder system consists.

In these cases, an inert liquid is used in step B. used, which is capable of the disperse phase of an emulsion or part of the disperse phase of an emulsion form, the continuous phase of the curable binder contains or consists of it, preferably water, especially for W / O emulsions.

Any fillers can be used according to the invention, as long as they shape and harden the binder do not interfere.

Examples of suitable granular ones that can be used in step A. Fillers are inorganic and / or organic fillers, especially carbon black, graphite, chalk, gypsum, cement, aluminum oxide, Aluminum hydroxide, kaolin, phosphates, ammonium polyphosphate, Montmorillonite, expanded minerals, in particular Clays, silicates or glass, and / or organic polymer particles, especially foamed polymer particles, such as polystyrene or polyurethane foam particles.

The term 'inert' means in connection with the in Step B liquid introduced into the mold so that this per se with the resin system introduced into the mold in step C. does not react and neither an inhibiting nor a catalyzing Has an effect and possibly also a binder emulsion does not break. However, the inert liquid can may contain additives that have such effects, in particular Hardener and / or hardening accelerator.

In addition to water, any other liquids are also suitable, especially organic liquids.

The inert liquid can also contain other additives, which serve to adjust the solvency, or about surfactant to improve wetting of the Filler.

The expression 'low viscosity' is intended to express that the inert liquid has a sufficiently low viscosity has to the grain spaces and other empty spaces in fill the form in step B as completely as possible and to be able to fill, and thus the filling and emptying process can proceed sufficiently quickly. Choosing one inert liquid with a suitable viscosity for a given curing temperature, which is essentially from the resin system depends on the skill level.

The granular filler used in step A has preferably a grain size in the range of about 1 to about 16 mm and more preferably in the range of about 2 to about 8 mm and preferably has a bulk density ≤ 1.5 g / ml.

The bulk density (apparent density) is preferred ≤ 1.0 g / ml.

According to a further preferred embodiment of the invention The inert liquid and the process Resin system, including the respective additives, chosen so that in step C an emulsion with the forms inert liquid as a disperse phase or such Emulsion is completed. It can preferably that in step C in the mold or on and between the filler particles remaining portion of inert liquid for Serve formation of the emulsion.

Steps B, C, and D are preferably closed Form performed.

Because the curing speed and thus the curing time of the resin system in step D for a given amount of hardener essentially depend on the temperature, in many cases it is favorable, the shape and the filler contained therein through an appropriately tempered inert liquid bring a desired temperature, so that, if necessary, by Add appropriately tempered binder in step C to set a desired reaction temperature.

The hardener for the resin system, which is not preferred in advance mixed the resin, but in step C from a separate Storage container in an upstream of the mold inlet Mixing chamber is metered to the inflowing resin is preferred liquid. However, it can also be used as a solution or in a Emulsion present. In the context of the invention, the hardener but also in a separate upstream step mixed with the resin, then the reacting mixture is introduced into the mold. The resin system can also contain additives included, which are common in the field of casting resins and are familiar to the expert. This also includes fillers. In contrast to the granular ones used in step A. These fillers are in the resin phase or in fillers In the case of a binder emulsion in one of the emulsion phases in front. The type and grain size of these fillers are not subject to any Limitation provided that they do not interfere with the hardening of the resin phase.

(i) eine Form,

(ii) einen ggf. mit der Form verbindbaren Vorratsbehälter für kornförmige Füllstoffe,

(iii) einen mit der Form verbindbaren Vorratsbehälter für eine niedrigviskose, mit dem Bindemittel nicht mischbare oder weitgehend nicht mischbare, gegenüber dem Bindemittel inerte oder im wesentlichen inerte Flüssigkeit,

(iv) einen mit der Form verbindbaren Vorratsbehälter für ein flüssiges, härtbares Bindemittel,

(v) eine Füll- und Entleereinrichtung, die mit dem Einlaß und dem Auslaß der Form und dem Vorratsbehälter für inerte Flüssigkeit, dem Vorratsbehälter für Bindemittel und dem Vorratsbehälter für Härter verbunden ist und die gesteuerte Zufuhr und Abführung der inerten Flüssigkeit und die gesteuerte Zufuhr des Bindemittels erlaubt,
und

(vi) eine Steuereinrichtung, welche die Füll- und Entleereinrichtung steuert und so ausgebildet ist, daß folgende Schritte durchführbar sind:

(a) Auffüllen der Form, die den Füllstoff enthält, mit der inerten Flüssigkeit bei gleichzeitiger oder nachgeschalteter Entlüftung der Form
und

(b) Einleiten des härtbaren Bindemittels und des Härters in die Form unter Ersatz der inerten Flüssigkeit.

The device according to the invention for the production of moldings based on a hardened binder which contains one or more granular fillers and which is particularly suitable for carrying out the method according to the invention has the following essential components:

(i) a shape

(ii) a storage container for granular fillers which may be connectable to the mold,

(iii) a storage container which can be connected to the mold for a low-viscosity liquid which is immiscible or largely immiscible with the binder and which is inert or essentially inert with respect to the binder,

(iv) a reservoir for a liquid, curable binder which can be connected to the mold,

(v) a filling and emptying device which is connected to the inlet and the outlet of the mold and the reservoir for inert liquid, the reservoir for binder and the reservoir for hardener and the controlled supply and discharge of the inert liquid and the controlled supply of the Binder allowed,
and

(vi) a control device which controls the filling and emptying device and is designed such that the following steps can be carried out:

(a) Filling the mold containing the filler with the inert liquid with simultaneous or downstream venting of the mold
and

(b) introducing the curable binder and hardener into the mold replacing the inert liquid.

Step (a) can also, as for method steps A and B explained, are carried out so that the mold with a previously prepared dispersion or suspension of the filler is filled in the inert liquid.

The filling and emptying device and the control device the device according to the invention are preferably designed such that they also control the supply of the filler the reservoir for the filler into the mold before step (a) Allow via an appropriate feed device.

According to a further preferred embodiment, the control device trained to control the Hardening of the binder after step (b) according to time and / or Temperature allowed.

Is particularly preferred in the device according to the invention one connected to the mold and the filling and emptying device Mixing chamber provided with the reservoir for binders and the storage container for hardener and if necessary also with the reservoir for filler and if necessary with the Storage container for inert liquid is connected and in the residence time, especially the binder, is short enough is to blockages caused by polymerization or crosslinking or to prevent incrustations.

The filling and emptying device and the control device are also advantageously designed so that the supply the inert liquid from a reservoir into the outlet the shape and the discharge of the inert liquid Allow the mold to return to the reservoir via a pump.

The control device is advantageously a microcomputer system with a central processing unit (CPU), a Read / write memory (RAM), a read-only memory (ROM) and a bus system based on a specified or predefinable program the filling and emptying device controls through which steps (a) and (b) or process steps A, B, C and / or D can be controlled.

The control unit may also include an input unit, e.g. on Keyboard or another keyboard, as well as a display device, e.g. have a screen, which input information, e.g. Process information and other operationally relevant Information. Furthermore, an output unit be provided, e.g. a printer that provides information for logging, can be printed out.

After removal from the mold, the molding obtained is, if necessary dried, especially if to achieve a Porosity an emulsion, in particular a W / O emulsion used was, because the non-reactive, disperse phase, especially Water, generated by the placeholder effect during the hardening of pores.

The combination of a matrix from a W / O emulsion with the wet one granular filler is compared to the adhesion of the resin matrix in question on a dry filler surprisingly at least as good.

Processing in one is particularly advantageous closed system with monomeric W / O emulsions as a binder, formed in a closed container, stored and if necessary also with higher viscosity immediately can be supplied to the form.

According to one embodiment of the method, the inert Liquid to the mold and the filler heat is supplied and removed, to control the hardening process. After the inert Liquid is basically reusable, it can be used in a circuit in which the temperature is regulated becomes.

The method according to the invention offers compared to the prior art Technology essential advantages and new opportunities, especially in the production of larger molded parts when used of W / O emulsions.

Binder and granular filler remain until their Merge in step C separately. The curable binder advantageously contains a catalyst or a curing accelerator and can be stored prepared. The missing curing component is advantageous shortly before Insertion into the form e.g. added with a dosing pump and e.g. mixed in with a static mixer.

The form is filled with the binder in the Usually in a few minutes. Runs even at higher viscosity the binder evenly, the running or displaced following inert liquid into the mold. A complex mixing of binder and filler is therefore omitted according to the invention. The processing time is shortened and can Pot life of the binder can be easily adjusted. The curing of the binder takes place in the form. Residues or There is practically no loss of binder.

After only when introducing the binder into the mold exerted a little pressure on the already filled mold the design effort can be reduced to a minimum become.

It may also suffice already, one open to the top, after bottom with a drain with the grain shape Fill the filler and the inert liquid and then overlay with the binder, which so the drained at the same time or, to speed up the process, pumped inert liquid replaced.

According to the method of the invention can also be inexpensive Shaped body made with differently formed layers become. For example, plates can be produced are provided on both sides with a glass fiber mat are. For this, e.g. the glass fiber mats into shape brought that the filler is in between. The Glass fiber mats are perfectly integrated. Even layers with filler particles of different grain sizes and different densities are possible. The good integration of glass fiber mats proves that even with different Pour the granular fillers well into the matrix are to be integrated. Cavities or Elements for stiffening are provided.

In the case of the use of binders in the form of W / O emulsions can the water that is initially introduced into the mold if necessary, agents are added which stabilize the emulsion, W / O emulsifiers for improvement adhesion of the matrix, dispersed polymers to support the hardening reaction from the aqueous phase, water-soluble Compounds, formaldehyde sulfoxylate (rongalite), triethanolamine, as flame retardant or fire retardant sodium or potash water glass etc.

The W / O emulsion consists of a hardenable, liquid, with Water, optionally with the help of W / O emulsifiers, emulsifiable Binder under the influence of initiators and accelerators even in the presence of water is. Composition, manufacture and hardening of these W / O emulsions are known to the person skilled in the art; Examples are casting resins, such as polyester resins, epoxy resins, prepolymers of (meth) acrylates i.a. in emulsion form.

Polyester resins or polyester resin systems are particularly suitable.

In addition to water, the emulsion can contain powdered fillers such as e.g. Chalk, plaster, cement, aluminum hydroxide, kaolin, ammonium polyphosphate or water-soluble compounds, borax etc. included, provided this does not break the W / O emulsion. The viscosity of the emulsion must match the processing method be adjusted. This is also familiar to the person skilled in the art.

The W / O emulsion mixed with the various additives, if necessary must be flowable and stable so that it Pumping out or displacing the water in the space between the Penetrate particles of the granular filler and fill it can.

For the implementation of the method according to the invention the free spaces in the pile and the grain size of the Filler, which is preferably not less than about 2 mm should matter. Usually the filling is sufficient a shape with the resulting bulk density of the solid. An even distribution of the matrix is then obtained. The solid can be compressed in the mold, especially if when in the form of a suspension in the inert Liquid is introduced into the mold.

When using W / O emulsions, the ratio of Resin to water ranges from about 0: 0.1 to 1: 5.0 become (mass ratio).

The lower the water content of the emulsion, the greater can be the proportion of filler in the emulsion. The product characteristics can be from a polymer concrete to a change very fine-pored foam with special properties.

With the hardening of the resin emulsion starts from a ratio from water to resin proportions of about 1: 1 an open, with Water-filled microcellular product that after the Drying particularly favorable sound and heat insulating properties in addition to high mechanical strength. However, depending on the type of emulsifier, it is also possible to use one closed-pore matrix, which releases the water very slowly, to generate (e.g. with triethanolamine and a polyester casting resin).

The thermal conductivity for a cured and dried fine-porous product is, for example, at a density ≤ 0.3 g / ml 0.05; the compressive strength is approximately 2.0 to 18.0 N / mm ² . A weighted sound insulation value of 35 dB was found for 50 mm thick panels with a mass per unit area of 24 kg / m ² .

This shows that curable W / O emulsions are used as the binder medium due to their properties, particularly inexpensive to use Products result, not least because the resin content in the End product with granular fillers to a minimum (up to 6.0% by mass) can be reduced.

Heat and produced by the method according to the invention sound-absorbing, lightweight molded parts, e.g. for creation of partition walls are suitable due to their variable Properties and the low cost of manufacture can be used particularly cheaply in the construction sector.

The granular fillers become inorganic materials with a density of up to about 1.5 g / ml, a bulk density from about 0.15 g / ml and with grain sizes in the range from 1 to 16 mm preferred. However, the parameters mentioned can, if necessary can be easily changed. Such products are e.g. under the names expanded clay, expanded glass and Foam glass known. Basically you can use any materials are used as granular fillers if they are in the curable binder and largely in the inert liquid are insoluble.

The liquid binders can be finely branched with pressure Spaces one with granular material (e.g. a grain size of 2 to 4 mm) filled form bring, especially if they have higher viscosity and behave thixotropically.

Also by applying pressure and with simultaneous application of negative pressure on the opposite side of the mold is continuous Filling with coarser grain fillers only limited possible. The pressure loss increases with the degree of filling with emulsion always higher, and the pressure on the loose structure leads to a densification of the grain pile. Added to this are the emissions of Monomers and the loss of material. By the invention Procedures can have the significant disadvantages of previous ones Process for molding production eliminated and new, interesting Products are obtained that are suitable for numerous Applications.

The use of a largely closed is advantageous Systems. The hardenable part of the binder becomes storable prepared and only immediately after its use Dosing an accelerator into the packed with the filler and filled with the inert liquid, advantageous by draining or pumping off the inert Liquid from the mold.

The temperature can be determined by filling with the inert liquid regulated by form and filler and thus the hardening reaction to be controlled.

Agents can also be introduced via the inert liquid, those over those still present on the surface of the grains Residual moisture can take effect.

Especially when using W / O emulsions with casting resins is the quick, even and the filler pile not destructive exchange of inert liquid for binding agent completely surprising and essential for processing Significance because the filler in the end product is very even is distributed.

The procedure is generally any liquid Binder possible, that in the unavoidable Contact with the inert liquid and especially water is not decomposed or due to reactions not into the Gaps can penetrate.

The invention also includes those according to the invention Process available moldings, which are due to the novel manufacture structurally from to conventional Differentiate processes available moldings.

The invention also includes the use of the shaped articles, especially as building materials and for the production of building materials, especially as lightweight materials and for manufacturing of lightweight materials.

The method according to the invention and the device according to the invention are based on exemplary embodiments explained in more detail with reference to the drawings.

Figures 1 and 2 show devices according to the invention.

Fig. 1 shows the principle of the device according to the invention.

The device shown schematically in Fig. 1 comprises a Storage container 1 for the filler, a storage container 2 for the inert liquid, a storage container 3 for the binder and a storage container 4 for the hardener, the crosslinking agent or the like. .

The storage containers 2, 3, 4 are via valves 6, 7, 8 and corresponding lines connected to a mixing chamber 10, which is provided with a vent valve 9. The reservoir 1 is via a valve 5 with the shape 11 or in the form 11 opening upper line 16 connected.

The line 1 a should represent in schematic form that the Storage container 1 for the granular filler in any suitably connected or connectable to the mold 11 is. The storage container can e.g. either with the Mixing chamber 10 or with the upper line 16 or with a Opening of the mold 11 connected or connectable. The administration 1a can also represent a simple outlet from which the granular filler can be filled into the mold can.

The storage containers 1, 2 can also be combined in the form of a only storage container, which is then a filler dispersion contains or suspension and if necessary with a stirrer is equipped. The valves 5 and 6 are in this case replaced by a single valve.

The valve 5 is not absolutely necessary; whether it's provided depends on the design of the storage container 1 and the Operation of the device.

The mixing chamber 10 is connected to the upper one via the upper line 16 Connection of form 11 connected. The dismantled version Mold 11 has a molded jacket 12, an upper mold part 13 Mold lower part 14 and a bottom connection 15, which has a lower line 17 is connected to a valve 18 via that e.g. drain the inert liquid in the mold or can be pumped out. The outlet of the valve 18th can be connected to the reservoir 2, possibly via a Intermediate vessel. However, it can also be placed in any collecting container flow out.

The form 11 can be dismantled and has quick-action couplings on.

The valves 5, 6, 7, 8, 9 and 18 are with a control device 19 connected. The valves are preferably solenoid valves or motorized shut-off devices. The control device 19 controls valves 5, 6, 7, 8, 9 and / or 18 in such a way that part of process steps A to D or all process steps A to D are carried out automatically become.

The device according to the invention from FIG. 1 can of course be used also in the sense of the procedure for manual operation of the valves are operated. Then the control device 19 omitted.

The method of operation is described below using a W / O binder emulsion explained.

First, the form 11 with the filler from the reservoir 1 filled (step A). Then the form 11 with the inert liquid, in this case water, from which Storage container 2 via the valve 6 and the mixing chamber 10 filled, with the valve 9 is vented. The vent valve 9 can also be in another place in the upper Part of the form 11 may be provided. Alternatively, the storage container 2 via valve 6 also with the upper line 16 be connected.

The filling of the mold 11 containing the filler with water can alternatively also take place in such a way that water flows through the valve 18 from a storage container via the lower line 17 and the bottom connection 15 is pressed into the mold 11, for example with the help of a pump. In doing so, the Venting is particularly easy.

The shape 11 advantageously has at least in the area of the upper one or the lower connection for the upper or lower line 16 or 17 on a restraining member, e.g. a network, a Sieve or a sieve or perforated plate to rinse out Filler particles when filling mold 11 with the inert one To prevent liquid or the binder.

When the form 11 loaded with the filler contains the water is filled (step B), the water is filled with the binder replaced that from the reservoir 3 via the valve 7 is fed into the mixing chamber 10, where it consists of hardener the reservoir 4, which via the valve 8 and possibly a Dosing pump introduced or metered into the mixing chamber 10 becomes.

The reacting mixture, in the present example the O / W emulsion, passes from the mixing chamber 10 via the upper line 16 in the form 11, the water through the lower pipe 17 and the valve 18 is displaced (step C). A further ventilation is generally not required.

The binder then hardens in the Form 11 instead (step D). After the curing time is over the molded body formed after disassembling the mold 11 removed (Step E) and dried if necessary.

Because the water phase of the emulsion corresponds to its volume fraction Leaves voids in the finished, dried molded article, the molded body is more or less porous.

In this way, lightweight materials can be bought particularly cheaply produce with high thermal and acoustic insulation capacity, especially albeit fillers with a low apparent density, such as foamed or blown fillers.

The shape 11 can advantageously be designed so that quick and easy removal of the molded body in step E the line connections, e.g. the upper line 16 and the lower one Line 17, do not need to be removed or removed.

It is thus possible to produce shaped articles in a quasi-continuous manner at short intervals To establish operation.

Fig. 2 also shows schematically another according to the invention Device, the basic structure of which of Fig. 1st corresponds, the same elements having the same reference numbers are designated. This device also has storage containers 1, 2, 3 and 4 provided for the storage of Filler, inert liquid, binder or hardener are used.

The storage container 3 is via the valve 7 with a mixing container 29 connected, which is equipped with a stirring device is. In this mixing container 29, for example Binder emulsion can be produced. For this, in addition to the resin component, the other emulsion components and possibly Auxiliaries and additives are introduced into the mixing container 29.

The reservoirs 1 and 2 are via valves 5 and 6 respectively the lines 1a and 2a are connected to the mold 11. As above 1 in connection with line 1a suggest any suitable connection of the reservoir 1 with the form 11 is present. The same applies for the line 2a. The inert liquid can thus from the Storage container 2 via the valve 6 either in the premixing chamber 23 or in the mixing chamber 10 or in the upper line 16 or via another connection in the form 11 be initiated.

The outlet of the mixing container 29 is connected via a valve 24 a premixing chamber 23 connected to a vent valve 9 has. The premixing chamber is equipped with a Mixing chamber 10 connected via the upper line 16 with the same as in Fig. 1 constructed 11 in connection stands.

A light barrier 28 is arranged at the bottom connection 15 of the mold 11, which is the passage of the liquid / liquid phase boundary between the inert liquid and the binder and / or can detect the air / inert liquid phase boundary.

In the lower line 17 there is a motor-driven pump 21 arranged, the outlet side (pressure side) via the valve 18th and a flow meter to a reservoir 20, e.g. for inert liquid. The reservoir 20 has a heating device 26 with which its content brought to a selectable temperature or kept at it can be. For example, the temperature of the Filler and the shape and thus the curing process controlled become.

In the line connecting the valve 8 to the reservoir 4 for the hardener is also a motor-driven metering pump 22 provided with the hardener in the premixing chamber 23 can be metered.

This is used to carry out the method according to the invention Device e.g. operated as follows (example: use an O / W emulsion binder):

First, the mold 11 is filled with the filler (step A) which is then taken with water as an example of the inert liquid is filled and vented (step B). For an exit To prevent the filler from forming is a sieve 25 provided that in this mode of operation at least in the floor area the form 11 is arranged. For another, later Operating mode described, the sieve 25 can also in the upper Provided area or in both areas of the shape 11 his. It is by spacers 30 from the upper mold part 13 or spaced from the lower mold part 14.

The mesh size is chosen so that the grain-shaped Filler is retained.

If the mold 11 in step A first separately with the filler is filled, the shape can thus have two sieves 25, which in the area of the upper mold part 13 and in the area of Lower mold part 14 are provided.

When the mold 11 is filled with filler and water without bubbles is from the storage container 3, the binder, e.g. in Form of an O / W emulsion, via the valve 7 into the mixing container 29 initiated, from which it via the valve 24 into the premixing chamber 23 arrives where it is with the metering pump 22 and the valve 8 metered hardener is mixed. After passage the binder emulsion passes through the mixing chamber 10 into the form 11, from which it serves as the inert liquid Water displaced (step C) through the lower pipe 17 exits form 11 and e.g. with the pump 21 is suctioned off. The water passes through the valve 18 and Flow meter 27 in the reservoir 20 where it is stored or temporarily stored.

As mentioned above, the mixing container 29 can also serve to to produce a binder emulsion.

After the curing reaction (step D), the molded body removed from the mold 11 (step E) and dried if necessary.

The devices of FIG. 1 and FIG. 2 can also be different operated from the above description so that the inert liquid, here water, from a storage container (Fig. 2: reservoir 20) via the valve 18th and the pump 21, which then works in the reverse pumping sense (Fig. 2) and the lower line 17 through the bottom connection 15 is pressed into the mold 11, with the vent valve 9 is vented. In this case there is a Sieve 25 at least in the upper part of the mold 11, which previously with the filler was filled.

The introduction of the binder into Form 11 (step C) with replacement of the water can via the lower line 17th take place, in which case the displaced water from the top the shape via the mixing chamber 10 and the premixing chamber 23 (Fig. 2) and the vent valve can escape.

In all possible operating modes, the valves 5, 6, 7, 8, 9, 18 and / or 24 and the pumps 21 and 22, at 2 also the heating device 26 of the Storage container 20, controlled by the control device 19 be, with partial steps or the whole process of Steps A, B, C and D are controllable. Alternatively, manual operation is possible of the valves also possible.

Through additional heat e.g. after filling and gel formation in the form 11 removed from the device in one Water bath up to 95 ° C, with hot air, steam or through Microwave exposure can control the curing reaction that the use of fast accelerators is dispensed with can be.

With the help of the flow meter 27 in the lower line 17 determined and calculated values can be the required Amount of binder and the filling time for the mold determined taking into account the binder viscosity become. Alternatively, it is also possible to do this with the measured values to use a level sensor installed in the container 20.

Starting from the measured values determined with the flow meter 27 the valve 18 and thus the inflow and outflow of water in the mold 11 controlled. The light barrier 28 reports e.g. the leakage of binder and then causes the pump 21 to stop.

The construction of the device can be in essential parts be adapted to the respective use. It can be whole or only permanently installed in parts or locally independent, mobile be designed, the supply of inert liquid and Binder via flexible lines and manually operated fittings can be done.

1. Füllen der aus der Vorrichtung entnommenen Form mit kornförmigem Füllstoff (Schritt A).

2. Einsetzen der Form 11 in die Vorrichtung, Öffnen des Entlüftungsventils 9, Schließen des Ventils 24 und des Ventils 8.

3. Rückstellen des Durchflußmessers 27, Öffnen von Ventil 18, Anschalten der Pumpe 21.

4. Erwärmen des Wassers im Vorratsbehälter 20 mit der Heizeinrichtung 26 auf die gewünschte Temperatur. Eindrücken von Wasser in die Form 11 bis zum Austritt aus dem Entlüftungsventil 9, Abstellen der Pumpe 21. Über die zur Füllung der Füllstoffzwischenräume erforderliche Wassermenge, die der Bindemittelmenge entspricht, kann die notwendige Beschleuniger- oder Härtermenge, die über die Dosierpumpe 22 eingeführt wird, eingestellt werden (Schritt B).

5. Schließen des Entlüftungsventils 9, Öffnen von Ventil 8 (Beschleunigerzufuhr) und Ventil 24 (Bindemittelzulauf). Umschalten der Pumpe 21 auf Rücklauf. Die Pumpe 21 wird mit Erreichen des Nullwertes des Durchflußmessers 27 abgeschaltet (Schritt C).

6. Härtung.
Entnahme der Form 11 aus der Vorrichtung nach Vorhärtung bzw. Gelbildung; gegebenenfalls Ruhenlassen der Form unter Wärmeeinwirkung bis zur Durchhärtung (Schritt D).

7. Entnahme des Formkörpers aus der Form (Schritt E).

A typical work sequence is summarized, for example, as follows (Fig. 2):

1. Fill the mold removed from the device with granular filler (step A).

2. Insert the mold 11 into the device, open the vent valve 9, close the valve 24 and the valve 8.

3. Reset the flow meter 27, open the valve 18, switch on the pump 21.

4. Heating the water in the reservoir 20 with the heater 26 to the desired temperature. Pressing water into the mold 11 until it emerges from the vent valve 9, switching off the pump 21. About the amount of water required to fill the filler spaces, which corresponds to the amount of binder, the necessary amount of accelerator or hardener, which is introduced via the metering pump 22, can be set (step B).

5. Close the vent valve 9, open valve 8 (accelerator feed) and valve 24 (binder feed). Switching the pump 21 to return. The pump 21 is switched off when the flow meter 27 reaches the zero value (step C).

6. Hardening.
Removal of the mold 11 from the device after pre-hardening or gel formation; if necessary, let the mold rest under the influence of heat until it has hardened completely (step D).

7. Removal of the molded body from the mold (step E).

The valves can be controlled manually or electronically. Corresponding facilities are from cast resin technology known.

EXAMPLE 1

An open top box-shaped form 11 (Fig. 2) with the internal dimensions 70 cm x 50 cm x 8 cm comes with a grain-shaped Filler filled so that the surface of the filler package to the spacer 30 from the upper mold part 13 spaced sieve 25 adjacent. The fine mesh serving as a sieve Wire mesh keeps the filler with the filling Water back in its position. With a similar wire mesh the lower mold part 14 is covered. Form 11 will after filling with the filler via quick-release couplings connected to the rest of the device.

For filling the mold with an internal volume of 28 l 5700 g filler (grain size 2 to 4 mm, bulk density 0.19 g / ml, bulk density 0.29 g / ml) required. The amount of binder is 11.58 kg.

The binder is in the form of an O / W emulsion of the following composition: Emulsion: Resin content 22.5 mass% Resin / water ratio 1: 2.64 (by mass) No. component (G) (Dimensions-%) 1 Polyester resin 1940.05 16.87 2 Methyl methacrylate 647.45 5.63 3rd Emulsifier (W / O) 26.45 0.23 4th accelerator 26.45 (supplied via the metering pump 22) 0.23 5 water 6858.60 59.64 6 Martinal (aluminum hydroxide, grain size 40 µm flame retardant) 647.45 11.24 7 Durcal 40 (calcium carbonate, flame retardant) 1292.60 5.63 8th Harder 90.85 0.79 11529.90 100.00 (= 10293 ml)

The W / O emulsion with the components is in the mixing container 29 1-3 and 5-8 are formed. The mold 11 is filled with the filler and then closed.

With the pump 21 is heated from below to 25 ° C. depressed until it overflows at the vent valve 9 and thus simultaneously vented the mold and the filler pack. The valve 18 and the vent valve 9 are then closed.

Because of the filling quantity determined when filling the mold with water and filling time is the metering of accelerator or hardener set via the metering pump 22.

After venting, the mold is ready to absorb the binder. After opening the valve 24, the emulsion introduced from the mixing container 29 into the mold 11, the Accelerator metered via the metering pump 22 and the valve 8 will while the water is down over the bottom connection 15 expires. The filling of the form 11 with the emulsion is accelerated by switching on the pump 21. The pump 21 when the amount of emulsion corresponding to the amount of water is reached switched off. It took 3 minutes to fill.

The mold is removed from the device after 10 minutes with the bottom part solved, after which another, already filled form is inserted into the device.

The hardened molded part can be removed from the mold after 45 minutes. With the addition of heat, e.g. in a water bath (90 ° C), shortened the curing time to about 15 minutes.

After drying, the molded part loses approximately 99.5% of the water introduced with the emulsion, reaches a density of 0.36 g / ml, a compressive strength of 2.5 N / mm ² and a thermal conductivity of 0.1.

EXAMPLE 2

This example uses a filler with a larger grain size and glass fiber mats to reinforce the surfaces used.

A mold of the same type as in Example 1 is used, but is 2 cm narrower (internal dimensions 70 x 50 x 6 cm). The shape has a volume of 21 l. Required quantities Expanded clay 6825 g (grain size 4 to 8 mm, bulk density 0.325 g / ml, bulk density 0.625 g / ml) emulsion 10080 ml (9081 g) Emulsion: Resin content 20.17% by mass Resin / water ratio 1: 3.00 (related to mass) No. component (G) (Dimensions-%) 1 Polyester resin 1282.23 14.12 2 Methyl methacrylate 549.40 6.05 3rd Emulsifier (W / O) 27.24 0.30 4th accelerator 18.16 0.20 5 water 5500.36 60.57 6 Martinal (see example 1) 815.47 8.98 7 Durcal 40 (see example 1) 815.47 8.98 8th Harder 72.65 0.80 9080.98 g 100.00 (10078.8 ml)

A glass fiber mat (300 g / m ² ) is attached to each of the upper mold part 13 and the lower mold part 14 (each 50 x 70 cm). The filler is then filled in between the glass fiber mats. The further procedure corresponds to that of Example 1. The molded part is removed from the mold in 90 ° C. hot water after storage for 90 minutes. A solid plate is obtained; the glass fiber mats are perfectly integrated.

After drying for 14 days in air at a temperature of 14 to 20 ° C, the plate has a density (including the glass mats) of 0.56 g / ml, a compressive strength of 5.4 N / mm ² and a thermal conductivity of 0.09. With a mass per unit area of 24.0 kg / m ² , a weighted sound reduction index Rw of 35 dB was determined.

EXAMPLE 3

In this example, the water content of the used Emulsion reduced to a minimum, but the proportion finest grain fillers (especially aluminum hydroxide) elevated; further to further improve fire resistance Ammonium polyphosphate added.

The shape 11 (internal dimensions 70 x 50 x 6 cm) has a volume of 21 1. Expanded glass (grain size 2 to 4 mm, bulk density 0.19 g / ml, bulk density 0.29 g / ml) is used as the filler. Required quantities Expanded glass 3990 g (grain size 2 to 4 mm, bulk density 0.19 g / ml, bulk density 0.29 g / ml) emulsion 7241 ml (11430 g) Emulsion: Resin content 37.14% by mass Resin / water ratio 3.6: 1.00 (mass related) No. component (G) (Dimensions-%) 1 Polyester resin 3232.40 28.28 2 Methyl methacrylate 1012.70 8.86 3rd Emulsifier [W / O] 32.00 0.28 4th accelerator 32.00 via dosing pump 0.28 5 water 1175.00 10.28 6 Martinal 4245.10 37.14 7 Durcal 40 1362.45 11.92 8th Ammonium polyphosphate 211.45 1.85 9 Harder 126.87 1.11 11429.97 g 100.00 (7240.98 ml)

As in Example 1, after the filler has been introduced, the Form 11 filled with water (temperature 16 ° C) and vented; then, as previously described, the binder in the extent to which the water is drained or pumped out becomes.

The mold filled with the binder becomes from the device taken. The molded part is cured after 1 hour and is removed. After drying for 14 days at room temperature you get a very stable plate with a density of 0.69 g / ml. In addition to very good thermal insulation, the material exhibits a high compressive strength and good flame retardancy.

According to the present invention, not only those used Compounds and fillers and thus the most important Properties of the shaped bodies, such as thermal and acoustic insulation, mechanical strength and density, varied widely become; it is also possible e.g. by armoring with elements made of steel, wood, concrete or plastic or by reinforcing with fibers, nonwovens or flat textile materials, especially with glass fibers and glass fiber fabrics, manufacture high-strength molded parts. You can also by special shape and construction design, e.g. by involving of cavities or connecting elements, depending highly stable construction of the desired application and manufacture construction elements.

The moldings according to the invention are also particularly suitable as or for the production of formwork parts.

• Arbeiten in geschlossenem System bei geringstem Handhabungsaufwand
• Härtung über Temperatur der inerten Flüssigkeit steuerbar
• erhebliche Verkürzung der Härtungsdauer erzielbar
• praktisch keine Rückstandsprobleme, besonders bezüglich Harzrückständen, da in Vorrats- und Mischbehältern nur nichtreagierende Komponenten vorliegen
• Harze und insbesondere Emulsionssysteme praktisch ohne Verlust verarbeitbar.

Particular advantages of the procedure according to the invention are:

• Working in a closed system with minimal handling effort
• Hardening controllable via the temperature of the inert liquid
• considerable shortening of the curing time can be achieved
• practically no residue problems, especially with regard to resin residues, since only non-reactive components are present in storage and mixing containers
• Resins and especially emulsion systems can be processed practically without loss.

Legend to FIGS. 1 and 2

1

Storage container for granular filler

1a

Line for granular filler

2nd

Inert liquid reservoir

2a

Inert liquid line

3rd

Storage container binder (possibly emulsion or the like)

4th

Storage container hardener, crosslinking agent

5

Valve reservoir filler

6

Valve reservoir inert liquid

7

Valve storage container binder

8th

Valve storage container hardener

9

Vent valve

10th

Mixing chamber

11

shape

12th

Molded jacket

13

Molded top

14

Bottom part

15

Bottom connection of the form

16

top line

17th

bottom line

18th

Valve

19th

Control device

20th

Inert liquid reservoir

21

pump

22

Dosing pump

23

Premixing chamber

24th

Valve

25th

scree

26

heater

27

Flow meter

28

Photoelectric barrier

29

Mixing tank

30th

Spacers

Claims (16)

1. Process for producing mouldings from a hardened bonding material containing one or more granular fillers, consisting of

   Feeding of the granular filler or fillers and a liquid, hardenable bonding material into a mould,

   Hardening of the bonding material in the mould
   and

   Removal of the completed moulding from the mould, the process being characterised by the following process steps in sequence:

   (A) Feeding of the granular filler or fillers into the mould,

   (B) Filling of the mould with a low viscosity fluid, which is unmixable or substantially unmixable with the bonding material and which is inert or substantially inert with respect to the bonding material, by venting of the mould,

   (C) Replacement of the fluid in the mould with the liquid, hardenable bonding material,

   (D) Hardening of the bonding material, and

   (E) Removal of the moulding from the mould.
2. Process according to claim 1, characterised in that in step B the inert fluid is fed into the mould under hydrostatic pressure or pump pressure from above or from below the mould.
3. Process according to claims 1 or 2, characterised in that in step C

   (a) the bonding material is fed under hydrostatic pressure or pump pressure from above the mould and the inert fluid is allowed to drain out or is pumped out from the bottom of the mould or

   (b) the bonding material under hydrostatic pressure or pump pressure or by suction is fed into the mould from below and the inert fluid is allowed to run out or is pumped out from the top of the mould.
4. Process according to one or more of the claims from 1 to 3, characterised in that in step C the bonding material consists of a water-in-oil emulsion where the oil phase contains bonding material or consists entirely of bonding material.
5. Process according to one or more of the claims from 1 to 4, characterised in that in step C the bonding material consists of a polymerizable resin system containing one or more polymerizable monomers and also one or more polymerizable prepolymers.
6. Process according to one or more of the claims from 1 to 5, characterised in that in step C the bonding material consists of a polyester resin system, an epoxy resin system or a (meth)acrylate resin system.
7. Process according to one or more of the claims from 4 to 6, characterised in that in step B an inert fluid, preferably water, is used which is capable of forming the discontinuous phase of an emulsion or part of the discontinuous phase of an emulsion whose continuous phase contains or consists entirely of a hardenable bonding material.
8. Process according to one or more of the claims from 1 to 7, characterised in that step A uses an inorganic and/or organic granular filler consisting in particular of carbon black, graphite, chalk, gypsum, cement, aluminium oxide, aluminium hydroxide, kaolin, phosphate, ammonium polyphosphate, Montmorillonite, blown minerals, in particular clay, silicate or glass, and/or organic polymer particles and foamed polymer particles.
9. Device for producing mouldings from a hardened bonding material containing one or more granular fillers, and in particular designed to perform the process according to claims 1 to 8,and comprising the following components:

   (i) a mould (11),

   (ii) a storage tank (1) for granular filler, connected where necessary to the mould (11),

   (iii)a storage tank (2), connected to the mould (11), for low viscosity fluid which is unmixable or substantially unmixable with the bonding material and which is inert or substantially inert with respect to the bonding material,

   (iv) a storage tank (3), connected to the mould (11), for a liquid, hardenable bonding material,

   (v) a filling and drainage device (6, 7, 8, 9, 18) connecting the mould (11) inlet and outlet to the storage tank (2) for the inert fluid, to the storage tank (3) for the bonding material, and the storage tank (4) for the hardener, this device controlling the feeding and draining of the inert fluid and controlling the feeding of the bonding material and

   (vi) a control unit (19) controlling the filling and drainage device (6, 7, 8, 9, 18) so that the following process steps are performed:

   (a) filling the mould (11) containing filler with the inert fluid at the same time as, or after venting of the mould (11), and

   (b) feeding of the hardenable bonding material and the hardener into the mould (11) to take the place of the inert fluid.
10. Device according to claim 9, characterised in that the filling and drainage device (6, 7, 8, 9, 18) and the control unit (19) are designed so that they also permit controlled feeding of the filler from the storage container (1) to the mould (11) before step (a) by means of a feeding device (5).
11. Device according to claim 9 or 10, characterised in that the control unit (19) is designed so that it also permits control of the hardening of the bonding material after step (b) after a set time and/or temperature.
12. Device according to one or more of the claims from 9 to 11, characterised in that the device has a mixing chamber (10) connecting the mould (11) and the filling and drainage device (7, 8, 9, 18) to the storage tank (3) for the bonding material and the storage tank (4) for the hardener and, where required, to the storage tank (1) for the granular filler and, where necessary, to the storage tank (2) for the inert fluid.
13. Device according to one or more of the claims from 9 to 12, characterised in that the filling and drainage device (7, 8, 9, 17, 18) and the control unit (19) are designed so that they permit feeding of the inert fluid out of a storage tank (20) into the outlet of the mould (11) and also the drainage of the inert fluid out of the mould (11) back into the storage tank (20) by means of a pump (21).
14. Device according to one or more of the claims from 9 to 13, characterised in that the control unit (19) is a microprocessor system with a central processing unit (CPU), a random access memory (RAM), a read only memory (ROM) and a bus system which controls the filling and drainage device (5, 6, 7, 8, 9, 10, 18) according to an existing or prepared program.
15. Mouldings produced using the process according to one of the claims from 1 to 8.
16. Use of the mouldings according to claim 15 as building material or for the manufacture of building materials and in particular lightweight building material.

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